An iron(II)-catalyzed diastereoselective olefin aminofluorination is reported (dr up to >20:1). This new transformation applies a functionalized hydroxylamine and Et3N·3HF as the nitrogen and fluorine source, which facilitates the efficient synthesis of β-fluoro primary amines and amino acids from allylic alcohol derivatives. Preliminary mechanistic studies reveal that an iron-nitrenoid is a possible intermediate and that its reactivity and enantioselectivity can be efficiently modulated by ligands.